Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes

ABSTRACT

The present invention relates to particles that may be used to deliver materials, including but not limited to, laundry additives such as perfume materials; and detergent composition that contain such particles.

CROSS REFERENCE TO RELATED APPLICATIONS

This Application claims the benefit of PCT International ApplicationSer. No. PCT/IB00/01755, filed Nov. 27, 2000, which claims the benefitof U.S. Provisional Application Ser. No. 60/169,024 filed on Dec. 3,1999, (now abandoned); and U.S. Provisional Application No. 60/208,629,filed on Jun. 1, 2000, (now abandoned).

FIELD OF THE INVENTION

The present invention relates to delivery particles, particularly toparticles for the delivery of laundry additives, such as perfume agents,and detergent compositions including the delivery particles, especiallygranular detergents.

BACKGROUND OF THE INVENTION

Most consumers have come to expect scented laundry products and toexpect that fabrics which have been laundered also have a pleasingfragrance. In many parts of the world handwashing is the predominantmeans of laundering fabrics. When handwashing soiled fabrics the useroften comes in contact with the wash solution and is in close proximityto the detergent product used therein. Handwash solutions may alsodevelop an offensive odor upon addition of soiled clothes. Therefore, itis desirable and commercially beneficial to add perfume materials tosuch products. Perfume additives make laundry compositions moreaesthetically pleasing to the consumer, and in some cases the perfumeimparts a pleasant fragrance to fabrics treated therewith. However, theamount of perfume carryover from an aqueous laundry bath onto fabrics isoften marginal. Industry, therefore, has long searched for an effectiveperfume delivery system for use in detergent products which provideslong-lasting, storage-stable fragrance to the product, as well asreleases fragrance during use to mask wet solution odor and deliversfragrance to the laundered fabrics.

Further, after drying fabrics under the sun, fabrics obtain a “sun driedtype” of odor. Consumers often prefer this to a standard perfume odor.Also they often consider fabrics with these odors to be cleaner. Becauseconsumers like the odor, they like to dry fabrics under the sun. In somecountries, however, consumers cannot dry their fabrics outside becausethe air is not clean, or there is too much rain. As a result, they haveto dry their fabrics indoors and cannot expect to enjoy this benefit ofhaving a “sun-dried type” of odor on their fabrics.

A detergent composition comprising a perfume which can provide a“sun-dried type” of odor has now been found.

Laundry and other fabric care compositions which contain perfume mixedwith or sprayed onto the compositions are well known from commercialpractice. Because perfumes are made of a combination of volatilecompounds, perfume can be continuously emitted from simple solutions anddry mixes to which the perfume has been added. Various techniques havebeen developed to hinder or delay the release of perfume fromcompositions so that they will remain aesthetically pleasing for alonger length of time. To date, however, few of the methods deliversignificant fabric odor benefits after prolonged storage of the product.

Moreover, there has been a continuing search for methods andcompositions which will effectively and efficiently deliver perfume froma laundry bath onto fabric surfaces. As can be seen from the followingdisclosures, various methods of perfume delivery have been developedinvolving protection of the perfume through the wash cycle, with releaseof the perfume onto fabrics. U.S. Pat. No. 4,096,072, Brock et al,issued Jun. 20, 1978, teaches a method for delivering fabricconditioning agents, including perfume, through the wash and dry cyclevia a fatty quaternary ammonium salt. U.S. Pat. No. 4,402,856, Schnoringet al, issued Sep. 6, 1983, teaches a microencapsulation technique whichinvolves the formulation of a shell material which will allow fordiffusion of perfume out of the capsule only at certain temperatures.U.S. Pat. No. 4,152,272, Young, issued May 1, 1979, teachesincorporating perfume into waxy particles to protect the perfume throughstorage in dry compositions and through the laundry process. The perfumeassertedly diffuses through the wax on the fabric in the dryer. U.S.Pat. No. 5,066,419, Walley et al, issued Nov. 19, 1991, teaches perfumedispersed with a water-insoluble nonpolymeric carrier material andencapsulated in a protective shell by coating with a water-insolublefriable coating material. U.S. Pat. No. 5,094,761, Trinh et al, issuedMar. 10, 1992, teaches a perfume/cyclodextrin complex protected by claywhich provides perfume benefits to at least partially wetted fabrics.

Another method for delivery of perfume in the wash cycle involvescombining the perfume with an emulsifier and water-soluble polymer,forming the mixture into particles, and adding them to a laundrycomposition, as is described in U.S. Pat. No. 4,209,417, Whyte, issuedJun. 24, 1980; U.S. Pat. No. 4,339,356, Whyte, issued Jul. 13, 1982; andU.S. Pat. No. 3,576,760, Gould et al, issued Apr. 27, 1971. However,even with the substantial work done by industry in this area, a needstill exists for a simple, more efficient and effective perfume deliverysystem which can be mixed with laundry compositions to provide initialand lasting perfume benefits to fabrics which have been treated with thelaundry product.

The perfume can also be adsorbed onto a porous carrier material, such asa polymeric material, as described in U.K. Pat. Pub. 2,066,839, Bares etal, published Jul. 15, 1981. Perfumes have also been adsorbed onto aclay or zeolite material which is then admixed into particulatedetergent compositions. Generally, the preferred zeolites have been TypeA or 4A Zeolites with a nominal pore size of approximately 4 Angstromunits. It is now believed that with Zeolite A or 4A, the perfume isadsorbed onto the zeolite surface with relatively little of the perfumeactually absorbing into the zeolite pores. While the adsorption ofperfume onto zeolite or polymeric carriers may provide some improvementover the addition of neat perfume admixed with detergent compositions,industry is still searching for improvements in the length of storagetime of the laundry compositions without loss of perfumecharacteristics, in the intensity or amount of fragrance released duringthe wash process and delivered to fabrics, and in the duration of theperfume scent on the treated fabric surfaces.

Combinations of perfumes generally with larger pore size zeolites X andY are also taught in the art. East German Patent Publication No.248,508, published Aug. 12, 1987 relates to perfume dispensers (e.g., anair freshener) containing a faujasite-type zeolite (e.g, zeolite X andY) loaded with perfumes. The critical molecular diameters of the perfumemolecules are said to be between 2-8 Angstroms. Also, East German PatentPublication No. 137,599, published Sep. 12, 1979 teaches compositionsfor use in powdered washing agents to provide thermoregulated release ofperfume. Zeolites A, X and Y are taught for use in these compositions.These earlier teachings are repeated in the more recently filed Europeanapplications Publication No. 535,942, published Apr. 7, 1993, andPublication No. 536,942, published Apr. 14, 1993, by Unilever PLC, andU.S. Pat. No. 5,336,665, issued Aug. 9, 1994 to Garner-Gray et al.

Effective perfume delivery compositions are taught by WO 94/28107,published Dec. 8, 1994 by The Procter & Gamble Company. Thesecompositions comprise zeolites having pore size of at least 6 Angstroms(e.g., Zeolite X or Y), perfume releaseably incorporated in the pores ofthe zeolite, and a matrix coated on the perfumed zeolite, the matrixcomprising a water-soluble (wash removable) composition comprising from0% to about 80%, by weight, of at least one solid polyol containing morethan 3 hydroxyl moieties and from about 20% to about 100%, by weight, ofa fluid diol or polyol, in which the perfume is substantially insolubleand in which the solid polyol is substantially soluble.

Other perfume delivery systems are taught by WO 97/34982 and WO98/41607, published by The Procter & Gamble. WO 97/34982 disclosesparticles comprising perfume loaded zeolite and a release barrier, whichis an agent derived from a wax and having a size (i.e., across-sectional area) larger than the size of the pore openings of thezeolite carrier. WO 98/41607 discloses glassy particles comprisingagents useful for laundry or cleaning compositions and a glass derivedfrom one or more of at least partially-water-soluble hydroxyliccompounds. A preferred agent is a perfume in a zeolite carrier.

Another problem that may occur in providing perfumed products is theexcessive odor intensity associated with the products. A need thereforeexists for a perfume delivery system which provides satisfactory perfumeodor during use and thereafter from the dry laundered fabric, but whichalso provides prolonged storage benefits and reduced product odorintensity.

By the present invention it has now been discovered that perfume loadedinto porous carriers such as zeolite particles, can be effectivelyprotected from premature release of perfume by coating said loadedcarrier particles with a hydrophobic oil and thereafter encapsulatingthe oil-coated perfume-loaded carrier particles with a water-soluble orwater-dispersible, but oil-insoluble, material, such as starch ormodified starch. The porous carrier may be selected to be substantive tofabrics to be able to deposit enough perfume on the fabrics to deliver anoticeable odor benefit even after the fabrics are dry.

The present invention solves the long-standing need for a simple,effective, storage-stable perfume delivery system which providesconsumer-noticeable odor benefits during and after the launderingprocess, and which has reduced product odor during storage of thecomposition. In particular, fabrics treated by the present perfumedelivery system have higher scent intensity and remain scented forlonger periods of time after laundering and drying.

The present invention also provides a delivery system for otheradditives, which are desirably protected from release until the productcomprising the additive is exposed to a wet or moist environment.

SUMMARY OF THE INVENTION

The present invention relates to a delivery system for additives, whichare incorporated in a variety of consumer products, including detergentsand cleaning compositions, room deodorizers, insecticidal compositions,carpet cleaners and deodorizers wherein the additive is protected fromrelease until exposed to a wet or moist environment. Specifically, thepresent additive delivery system is a particle comprising a core of aporous carrier material containing an additive, such as a perfume, inits pores; a first coating of a hydrophobic oil encapsulating said core,and a second coating of a water-soluble or water ispersible, butoil-insoluble, material, such as starch or modified starch,encapsulating the hydrophobic-oil coated core. The present deliveryparticle can be used to deliver laundry and cleaning agents either to orthrough the wash cycle. A laundry additive delivery particle accordingto the present invention effectively delivers perfume ingredientsthrough the wash to a fabric surface.

In traditional perfume delivery systems more than 50% of the perfumematerial is “lost” due to diffusion of the volatile perfume materialsfrom the product or by dissolution in the wash, and is not delivered tothe fabric surface. In the present invention, the coatings effectivelyentrap the perfume material loaded into the carrier core. Thus, theperfume material is delivered to the fabric surface at a higher ratethrough the wash than with traditional perfume delivery systems.

The porous carrier material is typically selected from zeolites,macroporous zeolites, amorphous silicates, crystalline nonlayersilicates, layer silicates, calcium carbonates, calcium/sodium carbonatedouble salts, sodium carbonates, clays, sodalites, alkali metalphosphates, chitin microbeads, carboxyalkylcelluloses,carboxyalkylstarches, cyclodextrins, porous starches, and mixturesthereof. Preferably the carrier material is a zeolites such as ZeoliteX, Zeolite Y, and mixtures thereof.

Particularly preferred porous carriers are zeolite particles with anominal pore size of at least about 6 Angstroms to effectivelyincorporate perfume into their pores. Without wishing to be limited bytheory, it is believed that these zeolites provide a channel orcage-like structure in which the perfume molecules are trapped.Unfortunately, such perfumed zeolites are not sufficientlystorage-stable for commercial use in granular fabric care products suchas laundry detergents, particularly due to premature release of perfumeupon moisture absorption. However, it has now been discovered that theperfume-loaded zeolite can first be coated with a hydrophobic oil toprotect the zeolite particles by forming a protective barrier to entrapand maintain the perfume within the zeolite's pores, and thereafterencapsulating the oil-coated particle with a water-soluble orwater-dispersible, but oil-insoluble, material. Thus, the perfumesubstantially remains within the pores of the zeolite particles. It isalso believed that since the perfume is incorporated into the relativelylarge zeolite pores, it has better perfume retention through the laundryprocess than other smaller pore size zeolites in which the perfume ispredominately adsorbed on the zeolite surface.

The hydrophobic oil coating can be a non-perfume oil but is preferably aperfume which can be the same as or different from the perfume oilloaded into the carrier. It is believed that when the presentencapsulated particle is added to water, such as during laundering, thewater-soluble or water-dispersible encapsulating material dissolves andstarts to release the oil coating. When this oil coating is a perfume,the perfume notes are released from the wash solution, providing the wetodor benefit . The carrier particles loaded with perfume are released inthe wash solution and deposit onto fabrics. After the fabrics are dried,perfume is released from the carrier as moisture in the atmospheredisplaces the perfume contained in the pores of the carrier, providingthe dry odor benefit

The additive contained in the porous carrier core is preferably selectedfrom the group consisting of perfumes, bleaches, bleach promoters,bleach activators, bleach catalysts, chelants, antiscalants, dyetransfer inhibitors, photobleaches, enzymes, catalytic antibodies,brighteners, fabric-substantive dyes, antifungals, antimicrobials,insect repellents, soil release polymers, fabric softening agents, dyefixatives, pH jump systems, and mixtures thereof

The preferred laundry additive to be loaded into the porous carriermaterial is a perfume. Preferably, the particle core is a perfume-loadedzeolite (PLZ).

The preferred encapsulating material is a starch, modified starch orstarch hydrolysate while the preferred oil coating material is a perfumeoil. The external encapsulating material may further include aningredient selected from the group consisting of plasticizers,anti-agglomeration agents, and mixtures thereof.

In a further embodiment of the present invention, a laundry or cleaningdetergent composition is provided. The laundry or cleaning compositioncomprises from about 0.001% to about 50% by weight of the composition ofthe laundry additive particle as described above and from about 50% toabout 99.999% by weight of the composition of laundry ingredientsselected from the group consisting of detersive surfactants, builders,bleaching agents, enzymes, soil release polymers, dye transferinhibitors, fillers and mixtures thereof. Preferably, the compositionincludes at least one detersive surfactant and at least one builder.

Accordingly, it is an object of the present invention to provide anadditive delivery particle having a core loaded with an additive,preferably a laundry additive such as a perfume, and at least twosurface coatings comprising an intermediate hydrophobic oil coating andan external encapsulating coating of a water-soluble orwater-dispersible material. It is another object of the presentinvention to provide a laundry and cleaning composition having saidlaundry additive particle thereon. It is a further object of the presentinvention to provide a laundry additive particle which can provideimproved fabric odor benefits, prolong storage life capabilities, andreduce product odor intensity. These and other objects, features andadvantages of the present invention will be recognizable to one ofordinary skill in the art from the following description and theappended claims.

All percentages, ratios and proportions herein are on a weight basisunless otherwise indicated. All documents cited herein are herebyincorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a SEM of an intact average sized laundry additive particlecomprising an encapsulated perfume-loaded zeolite particle according tothe present invention.

FIG. 2 shows a SEM of a cross-section of a particle according to thepresent invention, containing loaded zeolite particles inside a starchcoating.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention relates to a laundry additive particle and tolaundry and cleaning compositions comprising the laundry additiveparticle, which is preferably a perfume-containing particle. Laundry andcleaning compositions include traditional granular laundry detergents aswell as granular bleach, automatic dishwashing, hard surface cleaning,and fabric softening compositions. The laundry additive particle of thepresent invention provides superior through the wash perfume deliverycapabilities as well as minimizes product odor due to evolving volatileperfume ingredients. While not wishing to be bound by theory, it is alsobelieved that the specified coatings of the particle of the presentinvention increase the stability of the particle.

The preferred laundry particle of the present invention comprises a coreof a porous carrier loaded with perfume, said loaded core being firstcoated with a hydrophobic oil material and thereafter encapsulated withan external coating of a water-soluble or water-dispersible, butoil-insoluble, material, such as starch or modified starch, to form thefinal particle.

Preferably, the laundry additive particles of the present invention havea hygroscopicity value of less than about 80%. The “hygroscopicityvalue”, as used herein, means the level of moisture uptake by theparticles, as measured by the percent increase in weight of theparticles under the following test method. The hygroscopicity valuerequired for the present invention particles is determined by placing 2grams of particles in an open container petri dish under conditions of90° F. and 80% relative humidity for a period of 4 weeks. The percentincrease in weight of the particles at the end of this time is theparticles' hygroscopicity value as used herein. Preferred particles ofthe present invention have a hygroscopicity value of less than about50%, more preferably less than about 30%.

The laundry additive particles of the present invention typicallycomprise from about 5% to about 50% of the loaded central core particlewhich itself is about 60% to about 99% porous carrier and about 1% toabout 40% perfume or other laundry additive material, from about 1% toabout 40% of hydrophobic oil intermediate coating material, and fromabout 10% to about 94% external encapsulating material.

Loaded Central Core Particle

As already stated, the central core of the additive particle comprises aporous carrier material and a laundry additive loaded into said carriermaterial. The two ingredients of the central core may be mixed in anumber of different ways.

At laboratory scale, basic equipment used for this purpose can vary froma 10-20 g coffee grinder to a 100-500 g. food processor or even a200-1000 g kitchen mixer. Procedure consists of placing the carriermaterial particles (zeolite) in the equipment and pouring the laundryadditive at the same time that mixing occurs. Mixing time is from 0.5 to15 minutes. The loaded carrier material (zeolite) is then allowed torest for a period from 0.5 to 48 hours before further processing. Duringthe loading process when heating occurs, cool jacketing may be used asan option. At pilot plant level, suitable equipment is a mixer of theLittleford type, which is a batch type mixer with plows and chopperblades that operate at high RPM's, to continuously mix the powder ormixture of powders while liquid perfume oil is being sprayed thereon.

Porous Carrier Material

The porous carrier material, as used herein, means any material capableof supporting (e.g., by adsorption into the pores) a deliverable agentsuch as a laundry or cleaning agent. Such materials include poroussolids such as zeolites.

Preferred zeolites are selected from zeolite X, zeolite Y and mixturesthereof The term “zeolite” used herein refers to a crystallinealumninosilicate material. The structural formula of a zeolite is basedon the crystal unit cell, the smallest unit of structure represented by

Mm/n[(AlO2)m(SiO2)y].xH2O

where n is the valence of the cation M, x is the number of watermolecules per unit cell, m and y are the total number of tetrahedra perunit cell, and y/m is 1 to 100. Most preferably, y/m is 1 to 5. Thecation M can be Group IA and Group IIA elements, such as sodium,potassium, magnesium, and calcium.

A zeolite useful herein is a faujasite-type zeolite, including Type XZeolite or Type Y Zeolite, both with a pore size typically in the rangeof from about 4 to about 10 Angstrom units, preferably about 8 Angstromunits.

The aluminosilicate zeolite materials useful in the practice of thisinvention are commercially available. Methods for producing X and Y-typezeolites are well-known and available in standard texts. Preferredsynthetic crystalline alumninosilicate materials useful herein areavailable under the designation Type X or Type Y.

For purposes of illustration and not by way of limitation, in apreferred embodiment, the crystalline aluminosilicate material is Type Xand is selected from the following:

Na₈₆[AlO₂]₈₆·(SiO₂)₁₀₆]·xH₂O,  (I)

K₈₆[AlO₂]₈₆·(SiO₂)₁₀₆]·xH₂O,  (II)

Ca₄₀Na₆[AlO₂]₈₆·(SiO₂)₁₀₆]·xH₂O,  (III)

Sr₂₁Ba₂₂[AlO₂]₈₆·(SiO₂)₁₀₆]·xH₂O,  (IV)

and mixtures thereof, wherein x is from about 0 to about 276. Zeolitesof Formula (I) and (II) have a nominal pore size or opening of 8.4Angstroms units. Zeolites of Formula (II) and (IV) have a nominal poresize or opening of 8.0 Angstroms units.

In another preferred embodiment, the crystalline aluminosilicatematerial is Type Y and is selected from the following(V)

Na₅₆[AlO₂]₅₆·(SiO₂)₁₃₆]·xH₂O,  (V)

K₅₆[AlO₂]₅₆·(SiO₂)₁₃₆]·xH₂O  (VI)

and mixtures thereof, wherein x is from about 0 to about 276. Zeolitesof Formula (V) and (VI) have a nominal pore size or opening of 8.0Angstroms units.

In yet another embodiment, the class of zeolites known as, “Zeolite MAP”may also be employed in the present invention. Such zeolites aredisclosed and described in U.S. patent application Ser. No. 08/716,147filed Sep. 16, 1996 and entitled, “Zeolite MAP and Alcalase for ImprovedFabric Care.”

Zeolites used in the present invention are in particle form having anaverage particle size from about 0.5 microns to about 120 microns,preferably from about 0.5 microns to about 30 microns, as measured bystandard particle size analysis technique.

The size of the zeolite particles allows them to be entrained in thefabrics with which they come in contact. Once established on the fabricsurface (with the coatings having been washed away during the laundryprocess), the zeolites can begin to release their incorporated laundryagents, especially when subjected to heat or humid conditions.

Intermediate Oil Coating Material

The intermediate oil coating material according to the present inventionforms a coating on the central core particle. The intermediate coatingprovides a barrier to minimize release or leakage of any deliverableagent, such as a perfume, incorporated into the porous carrier. Theintermediate coating material comprises a hydrophobic oil such as aperfume oil which can be the same as or different from the perfumeloaded into the carrier, or a non-perfume oil, such as mineral oil. Thehydrophobic oil can be one or a mixture of organic compounds, preferablyhaving a weighted average ClogP lower than the weighted average ClogP ofthe additive material or mixture loaded in the pores of the carrier.ClogP values are typically used to characterize perfume ingredients,i.e., by their octanol/water partition coefficient P. The octanol/waterpartition coefficient of a perfume ingredient is the ratio between itsequilibrium concentration in octanol and in water. The more hydrophobica material, the higher its ClogP. The intermediate oil coating materialis thus preferably less hydrophobic than the additive material containedin the porous carrier.

More preferably the highest ClogP of the material comprising thehydrophobic oil coating is lower than the lowest ClogP of the materialcomprising the additive loaded in the porous carrier. Even morepreferably, there is a difference of at least one unit and mostpreferably, two units between the highest ClogP of the hydrophobic oilcoating material and the lowest ClogP of the loaded additive material.

External Encapsulating Material

The external encapsulating material is coated on the intermediatecoating material which is coated on the core particle and provides theouter layer of the final particle. The external coating materialprovides a substantially non-tacky or non-sticky coating for the finalparticle. Preferably, the external coating provides a particle whichwill have a non-tacky surface in high humidity conditions such as 80%relative humidity at 90° F.

The external coating is a material derived from one or more at leastpartially wash-soluble or dispersible compounds. That is, the externalcoating will either be soluble in an aqueous wash environment or bedispersible in that aqueous wash environment. The compounds usefulherein are preferably selected from the following classes of materials.

1. Carbohydrates, which can be any or a mixture of: i) Starchesincluding modified starches and starch hydrolysates; ii)Oligosaccharides (defined as carbohydrate chains consisting of 2-35monosaccharide molecules); iii) Polysaccharides (defined as carbohydratechains consisting of at least 35 monosaccharide molecules); and iv)Simple sugars (or monosaccharides); and v) hydrogenates of i), ii),iii), and iv).

Both linear and branched carbohydrate chains may be used. In additionchemically modified starches and poly-/oligo-saccharides may be used.Typical modifications include the addition of hydrophobic moieties ofthe form of alkyl, aryl, etc. identical to those found in surfactants toimpart some surface activity to these compounds.

2. All natural or synthetic gums such as alginate esters, carrageenin,agar-agar, pectic acid, and natural gums such as gum arabic, gumtragacanth and gum karaya.

3. Chitin and chitosan.

4. Cellulose and cellulose derivatives. Examples include: i) Celluloseacetate and Cellulose acetate phthalate (CAP); ii) Hydroxypropyl MethylCellulose (HPMC); iii)Carboxymethylcellulose (CMC); iv) allenteric/aquateric coatings and mixtures thereof.

5. Silicates, Phosphates and Borates.

6. Water soluble polymers including polyacrylates, caprolactones,Polyvinyl alcohol (PVA) and Polyethylene glycol (PEG).

7. Waxes, including silicone waxes, paraffinic waxes, andmicrocrystalline waxes.

8. Plasticizers.

9. Long Chain (C₁₀-C₃₅) fatty compounds including fatty acids, fattyalcohols and fatty esters.

10. Natural proteins including gelatin, casein and egg albumin.

Materials within these classes which are not at least partially washsoluble or dispersible are useful herein only when mixed in such amountswith the compounds useful herein such that the particle produced has thepreferred hygroscopicity value of less than about 80%. It is alsopreferred that these compounds be low temperature processable,preferably within the range of from about 50° C. to about 200° C., andmore preferably within the range of from about 60° C. to about 180° C.

Preferred encapsulating materials are starches or modified starches suchas CAPSUL™ commercially available from National Starch, cellulose andcellulose derivatives such as hydroxy propyl methyl cellulose, othercarbohydrates such as sucrose and fructose, natural polymers such as gumarabic and guar gum, natural proteins, and water-soluble polymers suchas polyethylene glycol.

The external encapsulation coating may include optional additiveingredients such as plasticizers, anti-agglomeration agents, andmixtures thereof. The optional plasticizers include sorbitol,polyethylene glycol, propylene glycol, low molecular weightcarbohydrates and the like with a mixture of sorbitol and polyethyleneglycol and low molecular weight polyols being the most preferred. Theplasticizer is employed at levels of from about 0.01% to about 5%. Theanti-agglomeration agents according to the present invention arepreferably surfactants and are included at low levels of less than 1% ofthe external coating. Suitable surfactants for use in the presentinvention include TWEEN™ 80 commercially available from ImperialChemicals, Inc. (ICI).

Laundry and Cleaning Additives

Laundry and cleaning additives or agents are included in the particle ofthe present invention. The agents are contained in the porous carriermaterial as hereinbefore described. As can be appreciated for thepresent invention, agents which are incorporated into the particles ofthe present invention may be the same as or different from those agentswhich are typically used to formulate the remainder of the laundry andcleaning compositions containing the particle. For example, the particlemay comprise a perfume agent and (the same or different) perfume mayalso be blended into the final composition (such as by spray-ontechniques) along with the perfume-containing particle. These agents areselected as desired for the type of composition being formulated, suchas granular laundry detergent compositions, granular automaticdishwashing compositions, or hard surface cleaners.

The laundry particle of the present invention may of course be includedin a composition which may contain other ingredients. The compositionscontaining laundry additive particles can optionally include one or moreother detergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition (e.g.,perfumes, colorants, dyes, etc.).

Perfume

The preferred laundry or cleaning additive according to the presentinvention is a perfume material. As used herein the term “perfume” isused to indicate any odoriferous material which is subsequently releasedinto the aqueous bath and/or onto fabrics or other surfaces contactedtherewith. The perfume will most often be liquid at ambienttemperatures. A wide variety of chemicals are known for perfume uses,including materials such as aldehydes, especially C₆-C₁₄ aliphaticaldehydes, C₆-C₁₄ acyclic terpene aldehydes and mixtures thereof,ketones, alcohols and esters. More commonly, naturally occurring plantand animal oils and exudates comprising complex mixtures of variouschemical components are known for use as perfumes. The perfumes hereincan be relatively simple in their compositions or can comprise highlysophisticated complex mixtures of natural and synthetic chemicalcomponents, all chosen to provide any desired odor. Typical perfumes cancomprise, for example, woody/earthy bases containing exotic materialssuch as sandalwood, civet and patchouli oil. The perfumes can be of alight floral fragrance, e.g., rose extract, violet extract, and lilac.The perfumes can also be formulated to provide desirable fruity odors,e.g., lime, lemon, and orange. Any chemically compatible material whichexudes a pleasant or otherwise desirable odor can be used in theperfumed compositions herein.

If “sun dried” odor is the preferred odor, the perfume component isselected from the group consisting of C₆-C₁₄ aliphatic aldehydes, C₆-C₁₄acyclic terpene aldehyde and mixtures thereof. Preferably, the perfumecomponent is selected from C₈-C₁₂ aliphatic aldehydes, C₈-C₁₂ acyclicterpene aldehydes and mixtures thereof. Most preferably, the perfumecomponent is selected from the group consisting of citral; neral;iso-citral; dihydro citral; citronellal; octanal; nonanal; decanal;undecanal; dodecanal; tridecanal; 2-methyl decanal; methyl nonylacetaldehyde; 2-nonen-1-al; decanal; undecenal; undecylenic aldehyde; 2,6 dimethyl octanal; 2, 6, 10-trimethyl-9-undecen-1-al; trimethylundecanal; dodecenal; melonal; 2-methyl octanal; 3, 5, 5, trimethylhexanal and mixtures thereof. The preferable mixtures are, for example,a mixture comprising 30% by weight of 2-nonen-1-al, 40% by weight ofundecylenic aldehyde and 30% by weight of citral or a mixture comprising20% by weight of methyl nonyl acetaldehyde, 25% by weight of lauricaldehyde, 35% by weight of decanal and 20% by weight of 2-nonen-1-al.

By selecting a perfume component from among the foregoing, a “sun driedodor” is produced on the fabric even though the fabric is not actuallydried in the sun. The “sun dried” odor is formed by selecting aldehydessuch that at least one of them is present naturally in cotton fabricsafter the fabric is dried in the sun and thus, are a component of thesun dried odor.

Perfumes also include pro-fragrances such as acetal pro-fragrances,ketal pro-fragrances, ester pro-fragrances (e.g., digeranyl succinate),hydrolyzable inorganic-organic pro-fragrances, and mixtures thereof.These pro-fragrances may release the perfume material as a result ofsimple hydrolysis, or may be pH-change-triggered pro-fragrances (e.g.,pH drop) or may be enzymatically releasable pro-fragrances.

Preferred perfume agents useful herein are defined as follows.

For purposes of the present invention, perfume agents are those whichhave the ability to be incorporated into the pores of the carrier, andhence their utility as components for delivery from the carrier throughan aqueous environment. Commonly-owned WO 98/41607 describes thecharacteristic physical parameters of perfume molecules which affecttheir ability to be incorporated into the pores of a carrier, such as azeolite. Obviously for the present invention compositions wherebyperfume agents are being delivered by the compositions, sensoryperception is also required for a benefit to be seen by the consumer.For the present invention perfume delivery particles, the preferredperfume agents have a threshold of noticeability (measured as odordetection thresholds (“ODT”) under carefully controlled GC conditions asdescribed in detail hereinafter) less than or equal to 50 parts perbillion (“ppb”). Agents with ODTs above 50 ppb up to 1 part per million(“ppm”) are less preferred Agents with ODTs above 1 ppm are preferablyavoided. Laundry agent perfume mixtures useful for the present inventionperfume delivery particles preferably comprise from about 0% to about80% of deliverable agents with ODTs above 50 ppb up to 1 ppm, and fromabout 20% to about 100% (preferably from about 30% to about 100%; morepreferably from about 50% to about 100%) of deliverable agents with ODTsless than or equal to 50 ppb.

Also preferred are perfumes carried through the laundry process andthereafter released into the air around the dried fabrics (e.g., such asthe space around the fabric during storage). This requires movement ofthe perfume out of the zeolite pores with subsequent partitioning intothe air around the fabric. Preferred perfume agents are thereforefurther identified on the basis of their volatility. Boiling point isused herein as a measure of volatility and preferred materials have aboiling point less than 300° C. Laundry agent perfume mixtures usefulfor the present invention laundry particles preferably comprise at leastabout 50% of deliverable agents with boiling point less than 300° C.(preferably at least about 60%; more preferably at least about 70%).

In addition, preferred perfume delivery particles herein for use inlaundry detergents comprise compositions wherein at least about 80%, andmore preferably at least about 90%, of the deliverable perfume agentshave a weighted average ClogP value ranging from about 1.0 to 16, andmore preferably from about 2.0 to about 8.0. Most preferably, thedeliverable perfume agents or mixtures have a weighted average ClogPvalue between 3 and 4.5. While not wishing to be bound by theory, it isbelieved that perfume materials having the preferred ClogP values aresufficiently hydrophobic to be held inside the pores of the zeolitecarrier and deposited onto fabrics during the wash, yet are able to bereleased from the zeolite pores at a reasonable rate from dry fabric toprovide a noticeable benefit. ClogP values are obtained as follows.

Calculation of ClogP:

These perfume ingredients are characterized by their octanol/waterpartition coefficient P. The octanol/water partition coefficient of aperfume ingredient is the ratio between its equilibrium concentration inoctanol and in water. Since the partition coefficients of most perfumeingredients are large, they are more conveniently given in the form oftheir logarithm to the base 10, logP.

The logP of many perfume ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Information Systems,Inc. (Daylight CIS), contains many, along with citations to the originalliterature.

However, the logP values are most conveniently calculated by the “CLOGP”program, also available from Daylight CIS. This program also listsexperimental logP values when they are available in the Pomona92database. The “calculated logP” (ClogP) is determined by the fragmentapproach of Hansch and Leo (cf., A. Leo, in Comprehensive MedicinalChemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A.Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach isbased on the chemical structure of each perfume ingredient and takesinto account the numbers and types of atoms, the atom connectivity, andchemical bonding. The ClogP values, which are the most reliable andwidely used estimates for this physicochemical property, can be usedinstead of the experimental logP values in the selection of perfumeingredients.

Determination of Odor Detection Thresholds:

The gas chromatograph is characterized to determine the exact volume ofmaterial injected by the syringe, the precise split ratio, and thehydrocarbon response using a hydrocarbon standard of known concentrationand chain-length distribution. The air flow rate is accurately measuredand, assuming the duration of a human inhalation to last 0.2 minutes,the sampled volume is calculated. Since the precise concentration at thedetector at any point in time is known, the mass per volume inhaled isknown and hence the concentration of material. To determine whether amaterial has a threshold below 10 ppb, solutions are delivered to thesniff port at the back-calculated concentration. A panelist sniffs theGC effluent and identifies the retention time when odor is noticed. Theaverage over all panelists determines the threshold of noticeability.

The necessary amount of analyte is injected onto the column to achieve a10 ppb concentration at the detector Typical gas chromatographparameters for determining odor detection thresholds are listed below.

GC: 5890 Series II with FID detector

7673 Autosampler

Column: J&W Scientific DB-1

Length 30 meters ID 0.25 mm film thickness 1 micron

Method:

Split Injection: 17/1 split ratio

Autosampler: 1.13 microliters per injection

Column Flow: 1.10 mL/minute

Air Flow: 345 mL/minute

Inlet Temp. 245° C.

Detector Temp. 285° C.

Temperature Information

Initial Temperature: 50° C.

Rate: 5C/minute

Final Temperature: 280° C.

Final Time: 6 minutes

Leading assumptions: (i) 0.02 minutes per sniff

(ii) GC air adds to sample dilution

Particularly preferred perfumes for use in the present invention arethose perfumes referred to as high impact perfumes and characterized byhaving:

(1) a standard B.P. of about 275° C. or lower at 760 mm Hg, and;

(2) a ClogP, or an experimental logP, of about 2 or higher, and;

(3) an ODT of less than or equal to 50 ppb and greater than 10 ppb,

Perfume Fixative

Optionally, the perfume can be combined with a perfume fixative. Theperfume fixative materials employed herein are characterized by severalcriteria which make them especially suitable in the practice of thisinvention. Dispersible, toxicologically-acceptable, non-skin irritating,inert to the perfume, degradable and/or available from renewableresources, and relatively odorless additives are used. Perfume fixativesare believed to slow the evaporation of more volatile components of theperfume.

Examples of suitable fixatives include members selected from the groupconsisting of diethyl phthalate, musks, and mixtures thereof. If used,the perfume fixative comprises from about 10% to abut 50%, preferablyfrom about 20% to about 40%, by weight, of the perfume.

Incorporation of Perfume in Preferred Zeolite Carrier

The Type X or Type Y Zeolites to be used as the preferred carrier hereinpreferably contain less than about 15% desorbable water, more preferablyless than about 8% desorbable water, and most preferably less than about5% desorbable water. Such materials may be obtained by firstactivating/dehydrating by heating to about 150 to 350° C., optionallywith reduced pressure (from about 0.001 to about 20 Torr). Afteractivation, the agent is slowly and thoroughly mixed with the activatedzeclite and, optionally, heated to about 60° C. or up to about 2 hoursto accelerate absorption equilibrium within the zeolite particles. Theperfume/zeolite mixture is then cooled to room temperature and is in theform of a free-flowing powder.

The amount of perfume or other laundry additive incorporated into thezeolite carrier is typically from 1% to 40%, preferably at least about10%, more preferably at least about 18.5%, by weight of the loadedparticle, given the limits on the pore volume of the zeolite. It is tobe recognized, however, that the present invention particles may exceedthis level of laundry additive by weight of the particle, butrecognizing that excess levels of laundry additives will not beincorporated into the zeolite, even if only deliverable agents are used.Therefore, the present invention particles may comprise more than 40% byweight of laundry agents. Since any excess laundry agents (as well asany non-deliverable agents present) are not incorporated into thezeolite pores, these materials are likely to be immediately released tothe wash solution upon contact with the aqueous wash medium.

Coating and Encapsulation of Loaded Zeolite Particles

In an embodiment of the present invention, perfume-loaded zeoliteparticles in the form of a free-flowing powder are thoroughly coatedwith a hydrophobic oil such as mineral oil or perfume oil. Thehydrophobic-oil coated particles are mixed to a solution of modifiedstarch (CAPSUL™, National Starch & Chemicals) and agitated to form anemulsion. The emulsion is then spray-dried using a spray dryer having aspraying system such as co-current with a spinning disk, with vanelessdisk, with vaned disk or wheel or with two-fluid mist spray nozzle.Typical conditions involve an inlet temperature of from about 120° C. toabout 220° C. and an outlet temperature of from about 50° C. to about220° C.

The present laundry additive delivery particles are discrete particleshaving particle size of from about 3 to about 100 microns as measured bystandard particle size analysis technique. FIG. 1 shows a SEM of anintact average sized encapsulated perfume-loaded zeolite particleaccording to the present invention. FIG. 2 shows a cross-section of aparticle according to the present invention, containing loaded zeoliteparticles inside a starch coating.

Stability Testing of Encapsulated Perfume-Loaded Zeolite Particles

Samples of encapsulated perfume-loaded zeolite particles are kept inopen jars at 80° F. and 70% Relative Humidity and in sealed plastic bagsat 120° F. for ten days. After that period the samples are taken out andevaluated organoleptically. Particles are homogenized and dosedaccording to regional real washing conditions. They are mixed withodorless base granule, previously approved for this kind of test.Original particles (which are not subjected to stability testingconditions) are included as reference. Perfume intensity scores for theparticles are registered in terms of Dry Fabric Odor. Particles withperfume loaded zeolite arc able to provide between 5 points to 20 pointsof advantage, in a perfume intensity scale, compared against controlwith sprayed on perfume alone.

Adjunct Laundry or Cleaning Ingredients

Adjunct ingredients useful in the laundry or cleaning compositionsaccording to the present invention include surfactants, builders, andagents such as those which are incorporated into the present deliveryparticles. The various types of agents useful in laundry and cleaningcompositions are described hereinafter. The compositions containingparticulate compositions can optionally include one or more otherdetergent adjunct materials or other materials for assisting orenhancing cleaning performance, treatment of the substrate to becleaned, or to modify the aesthetics of the detergent composition.

Detersive Surfactant

The granules and/or the agglomerates include surfactants at the levelsstated previously. The detersive surfactant can be selected from thegroup consisting of anionic surfactants, nonionic surfactants, cationicsurfactants, zwitterionic surfactants and mixtures. Nonlimiting examplesof surfactants useful herein include the conventional C₁₁-C₁₈ alkylbenzene sulfonates (“LAS”) and primary, branched-chain and randomC₁₀-C₂₀ alkyl sulfates (“AS”), the C₁₀-C₁₈ secondary (2,3) alkylsulfates of the formula CH₃(CH₂)_(x)(CHOSO₃ ⁻M⁺) CH₃ and CH₃(CH₂)_(y)(CHOSO₃ ⁻M⁺) CH₂CH₃ where x and (y+1) are integers of at leastabout 7, preferably at least about 9, and M is a water-solubilizingcation, especially sodium, unsaturated sulfates such as oleyl sulfate,the C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxysulfates), C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1-5ethoxycarboxylates), the C_(10-C) ₁₈ glycerol ethers, the C₁₀-C₁₈ alkylpolyglycosides and their corresponding sulfated polyglycosides, andC₁₂-C₁₈ alpha-sulfonated fatty acid esters. If desired, the conventionalnonionic and amphoteric surfactants such as the C₁₂-C₁₈ alkylethoxylates (“AE”) including the so-called narrow peaked alkylethoxylates and C₆-C₁₂ alkyl phenol alkoxylates (especially ethoxylatesand mixed ethoxy/propoxy), C₁₂-C₁₈ betaines and sulfobetaines(“sultaines”), C₁₀-C₁₈ amine oxides, and the like, can also be includedin the overall compositions. The C₁₀-C₁₈ N-alkyl polyhydroxy fatty acidamides can also be used. Typical examples include the C₁₂-C₁₈N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactantsinclude the N-alkoxy polyhydroxy fatty acid amides, such as C₁₀-C₁₈N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C₁₂-C₁₈glucamides can be used for low sudsing. C₁₀-C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀-C₁₆soaps may be used. Mixtures of anionic and nonionic surfactants areespecially useful. Other conventional useful surfactants are listed instandard texts.

The C₁₀-C₁₈ alkyl alkoxy sulfates (“AE_(x)S”; especially EO 1-7 ethoxysulfates) and C₁₂-C₁₈ alkyl ethoxylates (“AE”) are the most preferredfor the cellulase-containing detergents described herein.

Detersive Builder

The granules and agglomerates preferably include a builder at thepreviously stated levels. To that end, inorganic as well as organicbuilders can be used. Also, crystalline as well as amorphous buildermaterials can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils and toeliminate water hardness.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and alumninosilicate. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“under built” situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck NaSKS-6 isthe trademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂SiO₅ morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x)O_(2x+1)·yH₂O wherein M is sodium or hydrogen,x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to20, preferably 0 can be used herein. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, betaand gamma form is. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) ismost preferred for use herein. Other silicates may also be useful suchas for example magnesium silicate, which can serve as a crispening agentin granular formulations, as a stabilizing agent for oxygen bleaches,and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973. As mentioned previously, aluminosilicatebuilders are useful builders in the present invention. Aluminosilicatebuilders are of great importance in most currently marketed heavy dutygranular detergent compositions, and can also be a significant builderingredient in liquid detergent formulations. Aluminosilicate buildersinclude those having the empirical formula:

M_(z)(zAlO₂)_(y)]·xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “polycarboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964. andLamberti et al, U.S. Pat. No. 3,635,830. issued Jan. 18, 1972. See also“TMS/TDS” builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, the various alkali metal,ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅-C₂₀ allyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where pbosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphqnate builders such as ethane 1hydroxy-1,1-diphosphonate and other known phosphonates (see, forexample, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and3,422,137) can also be used.

Other Adjunct Ingredients

The composition of the present invention may also include enzymes,enzyme stabilizers, brighteners, polymeric dispersing agents (i.e.polyacrylates), carriers, hydrotropes, suds boosters or suppressors,soil release agents, dye transfer inhibitors, and processing aids.

Granular Compositions

The laundry and cleaning compositions of the present invention can beused in both low density (below 550 grams/liter) and high densitygranular compositions in which the density of the granule is at least550 grams/liter. Granular compositions are typically designed to providean in the wash pH of from about 7.5 to about 11.5, more preferably fromabout 9.5 to about 10.5. Low density compositions can be prepared bystandard spray-drying processes. Various means and equipment areavailable to prepare high density compositions. Current commercialpractice in the field employs spray-drying towers to manufacturecompositions which have a density less than about 500 g/l. Accordingly,if spray-drying is used as part of the overall process, the resultingspray-dried particles must be further densified using the means andequipment described hereinafter. In the alternative, the formulator caneliminate spray-drying by using mixing, densifying and granulatingequipment that is commercially available. The following is a nonlimitingdescription of such equipment suitable for use herein.

Various means and equipment are available to prepare high density (i.e.,greater than about 550, preferably greater than about 650, grams/literor “g/l”), high solubility, free-flowing, granular detergentcompositions according to the present invention. Current commercialpractice in the field employs spray-drying towers to manufacturegranular laundry detergents which often have a density less than about500 g/l. In this procedure, an aqueous slurry of various heat-stableingredients in the final detergent composition are formed intohomogeneous granules by passage through a spray-drying tower, usingconventional techniques, at temperatures of about 175° C. to about 225°C. However, if spray drying is used as part of the overall processherein, additional process steps as described hereinafter must be usedto obtain the level of density (i.e., >650 g/l) required by moderncompact, low dosage detergent products.

For example, spray-dried granules from a tower can be densified furtherby loading a liquid such as water or a nonionic surfactant into thepores of the granules and/or subjecting them to one or more high speedmixer/densifiers. A suitable high speed mixer/densifier for this processis a device marketed under the tradename “Lödige CD 30” or “Le, ödige CB30 Recycler” which comprises a static cylindrical mixing drum having acentral rotating shaft with mixing/cutting blades mounted thereon. Inuse, the ingredients for the detergent composition are introduced intothe drum and the shaft/blade assembly is rotated at speeds in the rangeof 100-2500 rpm to provide thorough mixing/densification. See Jacobs etal, U.S. Pat. No. 5,149,455, issued Sep. 22, 1992. The preferredresidence time in the high speed mixer/densifier is from about 1 to 60seconds. Other such apparatus includes the devices marketed under thetradename “Shugi Granulator” and under the tradename “Drais K-TTP 80).

Another process step which can be used to densify further spray-driedgranules involves grinding and agglomerating or deforming thespray-dried granules in a moderate speed mixer/densifier so as to obtainparticles having lower intraparticle porosity. Equipment such as thatmarketed under the tradename “Lödige KM” (Series 300 or 600) or “LödigePloughshare” mixer/densifiers are suitable for this process step. Suchequipment is typically operated at 40-160 rpm. The residence time of thedetergent ingredients in the moderate speed mixer/densifier is fromabout 0.1 to 12 minutes. Other useful equipment includes the devicewhich is available under the tradename “Drais K-T 160”. This processstep which employs a moderate speed mixer/densifier (e.g. Lödige KM) canbe used by itself or sequentially with the aforementioned high speedmixer/densifier (e.g. Lödige CB) to achieve the desired density. Othertypes of granules manufacturing apparatus useful herein include theapparatus disclosed in U.S. Pat. No. 2,306,898, to G. L. Heller, Dec.29, 1942.

While it may be more suitable to use the high speed mixer/densifierfollowed by the low speed mixer/densifier, the reverse sequentialmixer/densifier configuration is also contemplated by the invention. Oneor a combination of various parameters including residence times in themixer/densifiers, operating temperatures of the equipment, temperatureand/or composition of the granules, the use of adjunct ingredients suchas liquid binders and flow aids, can be used to optimize densificationof the spray-dried granules in the process of the invention. By way ofexample, see the processes in Appel et al, U.S. Pat. No. 5,133,924,issued Jul. 28, 1992 (granules are brought into a deformable state priorto densification); Delwel et al, U.S. Pat. No. 4,637,891, issued Jan.20, 1987 (granulating spray-dried granules with a liquid binder andaluminosilicate); Kruse et al, U.S. Pat. No. 4,726,908, issued Feb. 23,1988 (granulating spray-dried granules with a liquid binder andaluminosilicate); and, Bortolotti et al, U.S. Pat. No. 5,160,657, issuedNov. 3, 1992 (coating densified granules with a liquid binder andaluminosilicate).

In those situations in which particularly heat sensitive or highlyvolatile detergent ingredients are to be incorporated into the finaldetergent composition, processes which do not include spray dryingtowers are preferred. The formulator can eliminate the spray-drying stepby feeding, in either a continuous or batch mode, starting detergentingredients directly into mixing/densifying equipment that iscommercially available. One particularly preferred embodiment involvescharging a surfactant paste and an anhydrous builder material into ahigh speed mixer/densifier (e.g. Lödige CB) followed by a moderate speedmixer/densifier (e.g. Lödige KM) to form high density detergentagglomerates. See Capeci et al, U.S. Pat. No. 5,366,652, issued Nov. 22,1994 and Capeci et al, U.S. Pat. No. 5,486,303, issued Jan. 23, 1996.Optionally, the liquid/solids ratio of the starting detergentingredients in such a process can be selected to obtain high densityagglomerates that are more free flowing and crisp.

Optionally, the process may include one or more recycle streams ofundersized particles produced by the process which are fed back to themixer/densifiers for further agglomeration or build-up. The oversizedparticles produced by this process can be sent to grinding apparatus andthen fed back to the mixing/densifying equipment. These additionalrecycle process steps facilitate build-up agglomeration of the startingdetergent ingredients resulting in a finished composition having auniform distribution of the desired particle size (400-700 microns) anddensity (>550 g/l). See Capeci et al, U.S. Pat. No. 5,516,448, issuedMay 14, 1996 and Capeci et al, U.S. Pat. No. 5,489,392, issued Feb. 6,1996. Other suitable processes which do not call for the use ofspray-drying towers are described by Bollier et al, U.S. Pat. No.4,828,721, issued May 9, 1989; Beerse et al, U.S. Pat. No. 5,108,646,issued Apr. 28, 1992; and, Jolicoeur, U.S. Pat. 5,178,798, issued Jan.12,1993.

In yet another embodiment, the high density detergent composition of theinvention can be produced using a fluidized bed mixer. In this process,the various ingredients of the finished composition are combined in anaqueous slurry (typically 80% solids content) and sprayed into afluidized bed to provide the finished detergent granules. Prior to thefluidized bed, this process can optionally include the step of mixingthe slurry using the aforementioned Lödige CB mixer/densifier or a“Flexomix 160” mixer/densifier, available from Shugi. Fluidized bed ormoving beds of the type available under the tradename “Escher Wyss” canbe used in such processes.

Another suitable process which can be used herein involves feeding aliquid acid precursor of an anionic surfactant, an alkaline inorganicmaterial (e.g. sodium carbonate) and optionally other detergentingredients into a high speed mixer/densifier (residence time 5-30seconds) so as to form agglomerates containing a partially or totallyneutralized anionic surfactant salt and the other starting detergentingredients. Optionally, the contents in the high speed mixer/densifiercan be sent to a moderate speed mixer/densifier (e.g. Lödige KM) forfurther agglomeration resulting in the finished high density detergentcomposition. See Appel et al, U.S. Pat. No. 5,164,108, issued Nov. 17,1992.

Optionally, high density detergent compositions according to theinvention can be produced by blending conventional or densifiedspray-dried detergent granules with detergent agglomerates in variousproportions (e.g. a 60:40 weight ratio of granules to agglomerates)produced by one or a combination of the processes discussed herein.Additional adjunct ingredients such as enzymes, perfumes, brightenersand the like can be sprayed or admixed with the agglomerates, granulesor mixtures thereof produced by the processes discussed herein.Bleaching compositions in granular form typically limit water content,for example, to less than about 7% free water, for best storagestability.

Deposition of Perfume onto Fabric Surfaces

The method of washing fabrics and depositing perfume thereto comprisescontacting said fabrics with an aqueous wash liquor comprising at leastabout 100 ppm of conventional detersive ingredients describedhereinabove, as well as at least about 0.1 ppm of the above-disclosedlaundry additive particle. Preferably, said aqueous liquor comprisesfrom about 500 ppm to about 20,000 ppm of the conventional detersiveingredients and from about 10 ppm to about 200 ppm of the laundryadditive particle.

The laundry additive particle works under all circumstances, but isparticularly useful for providing odor benefits during the launderingprocess and on wet and dry fabrics. The method comprises contactingfabrics with an aqueous liquor containing at least about 100 ppm ofconventional detersive ingredients and at least about 1 ppm of thelaundry additive particle such that the perfumed zeolite particles areentrained on the fabrics, storing linedried fabrics under ambientconditions with humidity of at least 20%, drying the fabric in aconventional automatic dryer, or applying heat to fabrics which havebeen line-dried or machine dried at low heat (less than about 50° C.) byconventional ironing means (preferably with steam or pre-wetting).

The following nonlimiting examples illustrate the parameters of andcompositions employed within the invention. All percentages, parts andratios are by weight unless otherwise indicated.

EXAMPLE I

Perfume-loaded zeolite (“PLZ”) is prepared by mixing Zeolite 13X andperfume at a 85/15 weight ratio. The PLZ is thoroughly mixed with theintermediate coating oil (ICO) in a proportion of 1:0.5 to 1:1 PLZ:ICO.The mixture is then poured into a solution about 4 fold the weight ofthe mixture and containing about 25% solid starch. During the entireprocess, this second mixture is kept with agitation using a mixer or ahigh-speed homogenizer such as a tissue homogenizer. The mixture is thenpumped into a spray dryer at 180° C. to 220° C. The process yields afine powder, which is suitable for use as a laundry additive in adetergent composition. The perfume loaded in the zeolite has followingcomposition:

Material Name % Violiff 2.5 Frutene 15.0 Methyl Iso Butenyl 7.5Tetrahydro Pyran Cymal 10.0 Florhydral 15.0 Delta Damascone 15.0 IononeBeta 25.0 P.T. Bucinal 10.0

The particles formed unexpectedly have a superior “Neat Product Odor”(“NPO”) and emit only minimal detectable odors over the base productodor as observed by a statistically significant number of panelistgraders. This provides strong evidence of the lack of perfumedisplacement from the carrier particles.

EXAMPLE II

Several detergent compositions are exemplified below incorporating theperfume particle prepared in Example I.

A B C Base Granule Aluminosilicate 18.0 22.0 24.0 Sodium Sulfate 10.019.0 6.0 Sodium Polyacrylate Polymer 3.0 2.0 4.0 PolyethyleneGlycol (MW= 400) 2.0 1.0 — C₁₂₋₁₃ Linear Alkylbenzene 6.0 7.0 8.0 Sulfonate, NaC₁₄₋₁₆ Secondary Alkyl 3.0 3.0 — Sulfate, Na C₁₄₋₁₅ Alkyl Ethoxylated3.0 9.0 — Sulfate, Na Sodium Silicate 1.0 2.0 3.0 Brightener 24/47¹ 0.30.3 0.3 Sodium Carbonate 7.0 26.0 Carboxymethyl Cellulose — — 1.0DTPMPA² — — 0.5 DTPA³ 0.5 — — Admixed Agglomerates C₁₄₋₁₅ Alkyl Sulfate,Na 5.0 — — C₁₂₋₁₃ Linear Alkylbenzene 2.0 — — Sulfonate, Na SodiumCarbonate 4.0 — — Polyethylene Glycol (MW = 4000) 1.0 — — Admix SodiumCarbonate — — 13.0 C₁₂₋₁₅ Alkyl Ethoxylate 2.0 0.5 2.0 (EO = 7) C₁₂₋₁₅Alkyl Ethoxylate — — 2.0 (EO = 3) Perfume Spray-On 0.3 0.4 0.3 PerfumeParticles⁴ 0.5 0.5 0.5 Polyvinylpyrrolidone 0.5 — — PolyvinylpyridineN-oxide 0.5 — — Polyvinylpyrrolidone- 0.5 — — polyvinylimidazoleDistearylamine & Cumene 2.0 — — Sulfonic Acid Soil Release Polymer⁵ 0.5— — Lipolase Lipase (100,000 LU/I)⁶ 0.5 — 0.5 Termamyl Amylase (60KNU/g)⁶ 0.3 — 0.3 CAREZYME ® Cellulase 0.3 — — (1000 CEVU/g)⁶ Protease(40 mg/g)⁷ 0.5 0.5 0.5 NOBS⁸ 5.0 — — TAED⁹ — — 3.0 Sodium Percarbonate12.0 — — Sodium Perborate Monohydrate — — 22.0 Polydimethylsiloxane 0.3— 3.0 Sodium Sulfate — — 3.0 Miscellaneous (water, etc.) balance balancebalance Total 100 100 100 ¹Purchased from Ciba-Geigy ²DiethyleneTriamine PentaMethylene Phosophonic Acid ³Diethylene TriaminePentaacetic Acid ⁴From Example I ⁵Made according to U.S. Pat. No.5,415,807, issued May 16, 1995 to Gosselink, et al. ⁶Purchased from NovoNordisk A/S ⁷Purchased from Genencor ⁸Nonanoyloxybenzenesulfonate ⁹TetraAcetyl Ethylene Diamine

EXAMPLE III

The following detergent compositions according to the invention aresuitable for machine and bandwashing operations. The base granule isprepared by a conventional spray drying process in which the startingingredients are formed into a slurry and passed through a spray dryingtower having a counter current stream of hot air (200-400 C) resultingin the formation of porous granules. The remaining adjunct detergentingredients are sprayed on or added dry.

A B C Base Granule C₁₂₋₁₃ Alkylbenzene 19.0 18.0 19.0 Sulfonate, NaCationic Surfactant¹ 0.5 0.5 — DTPMPA² 0.3 — — DTPA³ — 0.3 — SodiumTripolyphosphate 25.0 19.0 29.0 Acrylic/Maleic Co-polymer 1.0 0.6 —Carboxymethylcellulose 0.3 0.2 0.3 Brightener 49/15/33⁴ 0.2 0.2 0.2Sodium Sulfate 28.0 39.0 15.0 Sodium Silicate (2.0R) 7.5 — — SodiumSilicate (1.6R) — 7.5 6.0 Admix Quantum (zinc phthalocyanine 2.0 2.0 2.0sulfonate) Sodium Carbonate 5.0 6.0 20.0 C₁₂₋₁₃ Alkly Ethoxylate 0.4 —1.2 (EO = 7) Savinase⁵ Protease (4KNPY/g) 0.6 — 1.0 Termamyl⁵ Amylase(60 KNU/g) 0.4 — — Lipolase⁵ Lipase (100,000 LU/I) 0.1 0.1 0.1 Sav/Ban⁵(6 KNPU/100 KNU/g) — 0.3 — CAREZYME ®⁵ Cellulase — 0.1 — (1000 CEVU/g)Soil Release Polymer⁶ 0.1 0.1 0.3 Perfume Spray-On 0.4 0.4 0.4 PerfumeParticles⁷ 1.5 1.5 2.0 Miscellaneous (water, etc.) balance balancebalance Total 100.0 100.0 100.0 ¹C12-14Dimethyl Hydroxyethyl QuaternaryAmmonium Compound ²Diethylene Triamine Pentamethylenephosphoric Acid³Diethylene Triamine Pentaacetic Acid ⁴Purchased from Ciba-Geigy⁵Purchased from Novo Nordisk A/S ⁶Made according to U.S. Pat. No.5,415,807 issued May 16, 1995 to Gosselink et al ⁷From Example I

EXAMPLE IV

The following detergent composition according to the invention is in theform of a laundry bar which is particularly suitable for handwashingoperations.

% Weight Coconut Fatty Alkyl Sulfate 30.0 Sodium Tripolyphosphate 5.0Tetrasodium Pyrophosphate 5.0 Sodium Carbonate 20.0 Sodium Sulfate 5.0Calcium Carbonate 5.0 Na_(1.9)K_(0.1)Ca(CO₃)₂ 15.0 Aluminosilicate 2.0Coconut Fatty Alcohol 2.0 Perfume Particle¹ 1.0 Perfume Spray-On 1.0Miscellaneous (water, etc.) Balance Total 100.0 ¹From Example I.

Having thus described the invention in detail, it will be clear to thoseskilled in the art that various changes may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification

What is claimed is:
 1. An additive delivery particle comprising: (i) acentral core particle, said core particle comprising a porous carriermaterial and an additive contained in the pores of said porous carriermaterial; said additive comprising a perfume; (ii) an intermediatecoating material coated on said central core particle, said intermediatecoating material comprising a hydrophobic oil material; and (iii) anexternal encapsulating material coated on said intermediate coatingmaterial, said external encapsulating material providing said additivedelivery particle with a substantially non-tacky surface; said externalcoating material comprising one or more at least partially wash solubleor dispersible compounds selected from the group consisting ofcarbohydrates, cellulose and cellulose derivatives, natural andsynthetic gums, silicates, borates, phosphates, chitin and chitosan,water soluble polymers, fatty compounds, and mixtures thereof.
 2. Anadditive delivery particle according to claim 1, wherein saidintermediate hydrophobic oil coating material has a ClogP lower than theClogP of the additive material contained in the porous carrier material.3. An additive delivery particle according to claim 2 comprising: (i)from about 5% to about 50% of said central core particle, said coreparticle comprising by weight of the core particle, from about 60% toabout 99% porous carrier material and from about 1% to about 40%additive material; (ii) from about 1% to about 40% said intermediatehydrophobic coating material; and (iii) from about 10% to about 94% saidexternal encapsulating material.
 4. An additive delivery particleaccording to claim 3 wherein said porous carrier material is a zeoliteselected from the group consisting of Zeolite X, Zeolite Y, and mixturesthereof.
 5. An additive delivery particle according to claim 3 whereinsaid additive loaded into said carrier is a perfume material.
 6. Anadditive delivery particle according to claim 3 wherein saidintermediate hydrophobic coating material is a perfume oil.
 7. Anadditive delivery particle according to claim 3 wherein said externalcoating material is a carbohydrate selected from starch, modified starchor starch hydrolysate.
 8. An additive delivery particle according toclaim 3 comprising: (i) from about 5% to about 50% of said central coreparticle, said core particle comprising by weight of the core particlefrom about 60% to about 99% zeolite as porous carrier material and fromabout 1% to about 40% perfume material; (ii) from about 1% to about 40%perfume oil as intermediate coating material; and (iii) from about 10%to about 94% starch or modified starch as external encapsulatingmaterial.
 9. An additive delivery particle according to claim 8 whereinsaid perfume material loaded into said zeolite carrier has a weightedaverage ClogP value between about 1.0 and about 16.0.
 10. An additivedelivery particle according to claim 8 wherein said perfume materialloaded into said zeolite carrier comprises a high impact perfumecharacterized by having: (1) a standard B.P. of about 275° C. or lowerat 760 mm Hg, and; (2) a ClogP, or an experimental logP, of about 2 orhigher, and; (3) an ODT of less than or equal to 50 ppb and greater than10 ppb.
 11. An additive delivery particle according to claim 8 whereinsaid perfume oil used as intermediate coating material comprises a highimpact perfume characterized by having: (1) a standard B.P. of about275° C. or lower at 760 mm Hg, and; (2) a ClogP, or an experimentallogP, of about 2 or higher, and; (3) an ODT of less than or equal to 50ppb and greater than 10 ppb.
 12. An additive delivery particle accordingto claim 8 comprising: (i) from about 10% to about 40% of said centralcore particle; (ii) from about 10% to about 30% perfume oil asintermediate coating material; and (iii) from about 30% to about 80%starch or modified starch as external encapsulating material.
 13. Alaundry or cleaning detergent composition comprising: a) from about0.001% to about 50% by weight of the composition of an additive deliveryparticle comprising: (i) a central core particle, said core particlecomprising a porous carrier material and an additive contained in thepores of said porous carrier material; said additive comprising aperfume; (ii) an intermediate coating material coated on said centralcore particle, said intermediate coating material comprising ahydrophobic oil material; and (iii) an external encapsulating materialcoated on said intermediate coating material, said externalencapsulating material providing said laundry additive delivery particlewith a substantially non-tacky surface; said external coating materialcomprising one or more at least partially wash soluble or dispersiblecompounds selected from the group consisting of carbohydrates, celluloseand cellulose derivatives, natural and synthetic gums, silicates,borates, phosphates, chitin and chitosan, water soluble polymers, fattycompounds, and mixtures thereof; and b) from about 50% to about 99.999%by weight of the composition of laundry ingredients selected from thegroup consisting of detersive surfactants, builders, bleaching agents,enzymes, soil release polymers, dye transfer inhibitors, fillers andmixtures thereof.